X-Ray Crysatllographic and Vibrational Spectroscopic Studies of Thorium Bromate Hydrate

Th(BrO3)3·H2O single crystals were grown from its aqueous solution at room temperature. Single crystal XRD, Raman and FTIR techniques were used to investigate the crystal structure. The crystal structure was solved by Patterson method. The as grown crystals are in monoclinic system with space group P21/c. The unit cell parameters are a = 12.8555(18) Å, b = 7.8970(11) Å, c = 9.0716(10) Å,  = 90°,  = 131.568° and  = 90° and unit cell volume is 689.1(2) Å3. Z = 8, R factor is 5.9. The Raman and FTIR studies indicate the lowering of symmetry of bromate anion from C3V to C1. Hydrogen bonds with varying strengths are present in the crystal. The centrosymmetric space group P21/c of the crystal is confirmed by the non-coincidence of majority of Raman and IR bands

KUBERNATH RAY KE LALITH NIBANDH

HINDI

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

Theory for the Photoacoustic Response to X-Ray Absorption

A microscopic theory is presented for the photoacoustic effect induced in solids by x-ray absorption. The photoacoustic effect results from the thermalization of the excited Auger electrons and photoelectrons. We explain the dependence of the photoacoustic signal S on photon energy and the proportionality to the x-ray absorption coefficient in agreement with recent experiments on Cu. Results are presented for the dependence of S on photon energy, sample thickness, and the electronic structure of the absorbing solid.

X-Ray spectra of superheavy and quasi-superheavy elements

We discuss the possibility of identifying superheavy elements from the observation of their M-shell x-ray spectra, which might occur during the collision of a superheavy element with a heavy target. The same question is discussed for the possible observation of the x-rays from the quasimolecule (quasi-superheavy element) which is formed during such a heavy-ion collision. It is shown that it is very difficult, if not impossible, to determine any information about the interesting quantum electrodynamical effects from the M-shell x-ray spectra of these quasimolecules.

Threshold behaviour of L x-ray excitation in Xe - Ag collisions

In the collision system Xe - Ag, the thresholds for excitation of quasimolecular L radiation and characteristic Ag L radiation have been found to lie at about 5 MeV and 1 MeV, respectively. These results are discussed on the basis of ab initio calculations of the screened interaction potential and the electron-correlation diagram.

Nuclear charge radii from X-ray transitions in muonic atoms of carbon, nitrogen and oxygen

Energies of muonic X-rays of the K-series of carbon, nitrogen and oxygen have been measured with an accuracy of about 15 eV. Root mean square radii of the nuclear charge distributions were deduced. The results 2.49±0.05 fm for carbon, 2.55 ±0.03 fm for nitrogen and 2.71 ±0.02 fm for oxygen are in good agreement at comparable accuracy with recent electron scattering data.

2D-3D Rigid-Body Registration of X-Ray Fluoroscopy and CT Images

The registration of pre-operative volumetric datasets to intra- operative two-dimensional images provides an improved way of verifying patient position and medical instrument loca- tion. In applications from orthopedics to neurosurgery, it has a great value in maintaining up-to-date information about changes due to intervention. We propose a mutual information- based registration algorithm to establish the proper align- ment. For optimization purposes, we compare the perfor- mance of the non-gradient Powell method and two slightly di erent versions of a stochastic gradient ascent strategy: one using a sparsely sampled histogramming approach and the other Parzen windowing to carry out probability density approximation. Our main contribution lies in adopting the stochastic ap- proximation scheme successfully applied in 3D-3D registra- tion problems to the 2D-3D scenario, which obviates the need for the generation of full DRRs at each iteration of pose op- timization. This facilitates a considerable savings in compu- tation expense. We also introduce a new probability density estimator for image intensities via sparse histogramming, de- rive gradient estimates for the density measures required by the maximization procedure and introduce the framework for a multiresolution strategy to the problem. Registration results are presented on uoroscopy and CT datasets of a plastic pelvis and a real skull, and on a high-resolution CT- derived simulated dataset of a real skull, a plastic skull, a plastic pelvis and a plastic lumbar spine segment.

L'Eusebia Rayó té la paraula. 'Eusebia Rayó tiene la palabra'.

Resumen en catalán

Spaceman Ray.

Cumple las necesidades de la Estrategia Nacional de Lectura, Programa Nacional de Estudios en Inglaterra y Gales, Idioma Inglés en Escocia de cinco a catorce años, y el plan de estudios común en Irlanda del Norte. Diseñado para combinar las habilidades básicas relacionadas con el aprendizaje de la lectura y la escritura. Texto en rima que ayuda a desarrollar en los niños de primaria la conciencia fonológica y fonética, y especialmente su capacidad de discriminar, deletrear, leer las vocales, y el fonema ay. Para seis a siete años.

Analytical methodologies based on X-Ray Fluorescence Spectrometry (XRF) and Inductively Couple Plasma Spectroscopy (ICP) for the assessment of metal dispersal around mining environments

La investigació que es presenta en aquesta tesi es centra en l'aplicació i millora de metodologies analítiques existents i el desenvolupament de nous procediments que poden ser utilitzats per a l'estudi dels efectes ambientals de la dispersió dels metalls entorn a les zones mineres abandonades. En primer lloc, es van aplicar diferents procediments d'extracció simple i seqüencial per a estudiar la mobilitat, perillositat i bio-disponibilitat dels metalls continguts en residus miners de característiques diferents. Per altra banda, per a estudiar les fonts potencials de Pb en la vegetació de les zones mineres d'estudi, una metodologia basada en la utilització de les relacions isotòpiques de Pb determinades mitjançant ICP-MS va ser avaluada. Finalment, tenint en compte l'elevat nombre de mostres analitzades per a avaluar l'impacte de les activitats mineres, es va considerar apropiat el desenvolupament de mètodes analítics d'elevada productivitat. En aquest sentit la implementació d'estratègies quantitatives així com l'aplicació de les millores instrumentals en els equips de XRF han estat avaluades per a aconseguir resultats analítics fiables en l'anàlisi de plantes. A més, alguns paràmetres de qualitat com la precisió, l'exactitud i els límits de detecció han estat curosament determinats en les diverses configuracions de espectròmetres de XRF utilitzats en el decurs d'aquest treball (EDXRF, WDXRF i EDPXRF) per a establir la capacitat de la tècnica de XRF com a tècnica alternativa a les clàssiques comunament aplicades en la determinació d'elements en mostres vegetals.

Improvements in the ray tracing of implicit surfaces based on interval arithmetic

Las superfícies implícitas son útiles en muchas áreasde los gráficos por ordenador. Una de sus principales ventajas es que pueden ser fácilmente usadas como primitivas para modelado. Aun asi, no son muy usadas porque su visualización toma bastante tiempo. Cuando se necesita una visualización precisa, la mejor opción es usar trazado de rayos. Sin embargo, pequeñas partes de las superficies desaparecen durante la visualización. Esto ocurre por la truncación que se presenta en la representación en punto flotante de los ordenadores; algunos bits se puerden durante las operaciones matemáticas en los algoritmos de intersección. En este tesis se presentan algoritmos para solucionar esos problemas. La investigación se basa en el uso del Análisis Intervalar Modal el cual incluye herramientas para resolver problemas con incertidumbe cuantificada. En esta tesis se proporcionan los fundamentos matemáticos necesarios para el desarrollo de estos algoritmos.